Vat dyestuff



Patented Oct. 27, 1953 VAT DYESTUFF Jacob Koch, Basel, and Walter Kern, Sissaeh, Switzerland, assignors to Ciba Limited, Basel, Switzerland, 2. Swiss firm N Drawing. Application May 22, 1950, Serial No. 163,571. In Switzerland July 21, 1949 1 Claim. '5

According to this invention a valuable vat dye-- stuff is made by reacting 1 mol of 1:8-dibenzoylamino-4:5-diamincanthraquinone with 2 mols of anthraquinone containing a halogen atom in the 2-position. inoanthraquinone used as starting material may be prepared by dinitrating th oxamic acid of 1:8 diaminoanthraquinone, splitting on the oxalic acid radicals, benzoylating the 2 amino groups in the 1- and 8-positions, and subsequently reducing the 2 nitro groups in the L and fi-positions.

For reacting the resulting starting material withanthraquinone containing a halogen atom in the 2-position there may be used, for example, z-chloranthraquinone. The reaction is advantageously conducted in the presence of a high boiling acid-binding. agent or inert diluent, such as nitrobenzene or naphthalene, referably with the addition of a catalyst known to favor the If formation of anthrimides, such as copper or copper salts, at a raised temperature.

An alternative process for making the same dyestuff consists in treating 4:5-di-( S-anthraquinonyl) amino 1:8 diamin'oanthra uinone with a benzoylating agent.

The starting material required for this alternative process can be made by reacting 1 mol of 4:5-diamino-1 8-dinitroanthraquinone with 2 mols of a ET-halogen anthraquinone, and subsequently reducing the nitro groups. The benzoylation can be carried out, for'example, by means of benzoyl chloride in a high boiling solvent or diluent.

The 128 dibenzoy1amin-o 4 :5-di-(B-anthraquinonyl)-aminoanthraquinone obtainable by The 1 t8 dibenzoylamino-z S-diarnthis invention is a valuable ,vat dyestufi which is distinguished, more especially, by an excellent fastness to light and also by good general properties of iastness. It is suitable for dyeing or printing a very wide variety-of fibers, especially cellulose fibers, such as cotton, linen, and artificial silk and staple fibers of regenerated cellulose.

The following examples illustrate the invention, the parts being by weight unless otherwise parts by volume being the same as that of the kilogram to the liter:

, Erample 1 stated and the relationship of parts by weight to 4 benzoyl compound which has separated in the form of yellow platelets is separated by filtering with suction, washed with nitrobenzene and with alcohol, and then dried. It melts at about 3768 C. The yield amounts to -85 per cent. of the theoretical yield.

27 parts of the resulting 1:8-dibenzoylamino- 4:5-dinitroanthraquinone are finely pulverized and heated to about C. in 486 parts of nitrobenzene. '12 parts of hydrazine hydrate ('per cent. pure) are added, whereupon the reaction mixture immediately becomes blue, and the whole is stirred for one hour at 90-100 C. After a further addition of 6 parts of hydrazine hydrate, the whole is stirred at -110 C. for one hour longer. r

The l :8-dibenzoylamino-4 5-diaminoanthraquinone, which crystallizes in the form of blue needles, is separated by filtering the mixture with suction while hot, and washed with nitrobenzene and with alcohol and then dried. The yield arnlounts to 85-90 per cent. of the theoretical y e d. J 3

In a finely'powdered state 14.3 parts of 1:8-dibenzoylamino 4:5 diaminoanthraquinone, 16

parts of 2-chloranthraquinone, 6 parts of anhydrous sodium acetate, 3 parts of magnesium oxide and 2 parts of cuprous chloride ar mixed with 190 parts of naphthalene. The mixture is heated and the melt is'stirred while gently boiling until the starting materials have disappeared. The whole is then allowed to cool to. 150 C., it is di-- luted with parts of monochlorobenzene, and stirred for one hour at Mil- C. After being cooled to about 90 C., the mixture is filtered with suction. The residue is purified by treating it in turn with monochlorobenzene, alcohol, dilute hydrochloric acid and water, and then dried. The

yielg amounts to 70-80 per cent. of the theoretical yiel r V i The dyestuif is a green-blue powder which dissolves in concentrated sulfuric acid with a pure blue coloration. It dyes cotton from a red-brown vat bluish olive green tints having excellent properties of fastness.

Example 2 In a finely powdered condition 16.4 parts of 1:8 diamino 4:5 dinitroanthraquinone, 29.1 parts of 2-chloranthraquinone, 10.6 parts of anhydrous sodium carbcnate, 5 parts of magnesium oxide and'3 parts of cuprous chloride are mixed of benzoyl chloride are added and stirring is continued for one hour while boiling gently. After cooling the whole to room temperature, the diwith 230 parts of naphthalene.

ing until the starting materials have disappeared.

Th mixture is heated and the melt is stirred while gently boili is diluted with monochlorobenzene and worked is added to a, dyebath containing in 1700 parts up in the manner described in the third paraor water 4 parts by volume of caustic soda soluph O Xample 1. The yield amounts to about tion of 36 B. and 2 parts of sodium hydrosul- 60-70 per cent. of the theoretical yield. fite, and then 100 parts of cotton are entered 22.2 parts of the resulting 1:8-dinitro-4:5-di- 5 into the bath at 40 C. 20 parts of sodium chq oanthraquinone in a ride are added after 15 minutes and dyeing is finely po e ndit are a Part5 w rriedon 813407- ,Csfor 011 22110111. @The cotof nitrobenzene-to about 410? C. There ar 'n-tonishthen squeezed,' oxidized in the-air, rinsed,

added at first 8 parts and after one hour a furacidified, again rinsed and, if desired, soaped at ther 4 parts of hydrazine hydrate (95 per cent.,;l01 ;the boil. The cotton is dyed a fast bluish-olive pure), and the product is worked up in themam green tint.

ner described in the second paragraph of "Ex- *What we claim is:

ample 1. The yield amouri tsgzo QO QShper cent. T-hevatldyestufiof the formula of the theoretical yield.

13.6 parts of finely powdered 1:8-diamino- .15 4:5 di (2 anthraquinonyl) eaminoanthraquinone are heated in 400 partsoi nitrobenzene to C., while stirring. "'7 parts 'ofbenzoyl chloride are added, and the whole is istirred gfor one hour while gently boiling. After cooling, 20

the'mixture is filtered with-suction, and the residue .is :washedwith nitrobenzene and with alcohol and then dried. The yieldwamounts to aboutflo-per cent. of the theoretical yield. The idyestufi r so obtained has properties: substantially 5 identical with those of the product obtainedias described the: third' paragraph of Example 1. It isobvious that .theproductssobtainedby ,either: of-= the above processes are contaminated by:slight amounts of-impurities, and it is iur- 0 other obvious that these impurities are different 1 ,dependingon' the process used. This mayresult a slightly difierent-appearance of the products WALTER'ZKERN' Jot theatwowprocesses and even: of thedyeings this made therewith; but neyerthelessthBpPIOdLlGtS References clted'mithe melon "patent are essentially the same. UNITED STATES-PATENTS Example. 3 *Nllzlgge55 K .-Name -Date i u r- -1.5; parts of the vatedyestufi obtained as-,. deppe June 25"1940 svcribed in-Example 1 .are-:vatted:at about.50.C. 4O FOREIGN PATENTS and with 6 parts by volume of caustic soda solu- Number ,fCountry QDate -..tion of 361 B. and-3 partsof-sodiumhydrosulfite 25,986 Great. Britain ;,or 1909 in 300 parts of water. The stock vat so prepared 206,728 Switzerland ,'Aug. 1939 

